Method for preparation of urethanated hydroxyalkane sulfonates

ABSTRACT

Alkane sulfonate carbamates are obtained as the result of reaction conducted between hydroxyalkane sulfonate and urea in an aromatic hydrocarbon solvent.

United States Patent [1 1 Tamai et al.

[ METHOD FOR PREPARATION OF URETHANATED HYDROXYALKANE SULFONATES [75]lnventors: Iwao Tamai; Kenji Yokoi, both of lshikawa-shi, Japan [73]Assignee: Lion Fat & Oil Co., Ltd., Tokyo,

Japan [22] Filed: Dec. 27, 1971 [21] App]. N0.: 212,638

[30] Foreign Application Priority Data Dec. 26, 1970 Japan 45/129627[52] U.S. Cl 260/482 C [51] Int. Cl .L C07c 125/04 June 26, 1973 PrimaryExaminer-Henry R. Jiles Assistant Examiner-Paul J. KillosAtt0meyWoodhams, Blanchard & Flynn [5 7] ABSTRACT Alkane sulfonatecarbamates are obtained as the result of reaction condncted betweenhydroxyalkane sulfonate and urea in an aromatic hydrocarbon solvent.

4 Claims, No Drawings METHOD FOR PREPARATION OF URETI-IANATEDIIYDROXYALKANE SULFONATES BACKGROUND OF THE INVENTION ducting reactionbetween hydroxyalkane sulfonate expressed by the following generalformula, (I) and urea:

wherein R represents alkyl radical, R represents hydrogen or alkylradical, (but the sum total of carbon atoms possessed by both R and R is3 21), R represents absence or alkylene having one to three carbonatoms, and M represents alkali metal, alkali earth metal, ammonium, orsubstituted ammonium.

As a rule, when reaction is conducted between alcohols and urea toobtain carbamic acid ester, the reaction temperature should be kepthigher than the decomposing point of urea, that is, usually above 120 C,from the reason that it is necessary to induce urea to decompositionfirst of all.

Moreover, said reaction very often requires a catalyst such as tinchloride, nickel chloride, copper acetate, zinc dust, or vanadiumpentoxide.

SUMMARY OF THE INVENTION The object of the present invention is toprovide a method for preparing carbamic acid ester of hydroxy alkanesulfonate, expresses by the foregoing general formula, (II) by means ofconducting reaction between hydroxyalkane sulfonate, expressed by theforegoing general formula, (I) and urea at a temperature in the range of100 180 C, preferably 120 140 C, within an organic solvent to beinactive on urethanation.

, Hydroxyalkane sulfonate-applicable to the present invention includeshydroxyalkane sulfonate produced from the preparation process ofa-olefin sulfonate too, besides, for instance, such hydroxyalkanesulfonate that is prepared by a synthesizing method, which is describedin pp. 2,917 2,926, vol 97 ofChemische Berichte."

So far as it concerns to the quantity of urea to be utilized in thepresent invention, it should be within the range of l 1.0 4.0,preferably 1: 1.2 3.0 in the hydroxyalkane sulfonate to urea molarratio.

The reaction solvent applicable urethanation should be an inert organicsolvent and this kind of organic solvent includes benzene, toluene,xylene and mixtures thereof. Urethanation according to the presentinvention can be performed either the atmospheric pressure, or under theincreased pressure; however it should be carried out at a temperaturewithin the range of 100- 180 C, preferably 120 140 C. Further, ashydroxyalkane sulfonate itself is possessed of a catalytic activity, sourethanation thereof does not necessarily require presence of catalyst.

Nevertheless, the presence of 0.001 5.0 percent by weight of at leastone member selected from the group consisting of tin chloride, nickelchloride, copper acetate, zinc dust (blue powder), and vanadiumtetraoxide is capable of promoting urethanation more smoothly.

Carbamic acid ester of hydroxy alkane sulfonate obtained fromurethanation according to the present invention is possessed of surfaceactivity, so that this compound can be utilized advantageously also asan effective component of a detergent, or an additive thereof.

In addition, when nuclear magnetic resonance spectrum of urethanatedproduct obtained by a method according to the present invention by meansof empolying dimethyl sulfoxide as a solvent, a signal from terminalNI-l of urethane, and a signal from methyne radical in the main chainthereof are detected at 3.70 and z;

PREFERRED EMBODIMENTS OF THE INVENTION The. following examples willfurther illustrate the present invention and enable other skilled in artto understand the invention more completely. It is to be understood,however, that the following examples are not to be construed aslimitations on the practice of the invention.

Example 1.

In a ml three-necked flask equipped with reflux condenser, stirrer andthermometer, 9.0 g (0.15 mole) of urea and 17.2 g (0.05 mole) of sodiumslat of 3-hydroxyhexadecane sulfonic acid were placed with 50 ml ofxylene. The thus obtained mixture was subjected to 20-hoursreflux, andthereafter xylene was distilled out therefrom under the reducedpressure, whereby was resulted a solid matter. Said solid matter wasrecrystallized twice from water-alcohol, and subsequently elementanalysis was done against thus obtained crystal, whereby the followingresults were obtained.

measured value theoretical value C: 52.79% 52.71% H: 8.82% 8.79% N'3.55% 3.62%

EXAMPLE 2.

In 100 ml three-necked flash equipped with reflux condenser, stirrer andthermometer, 6.0 g (0.1 mole) of urea, 0.06 g of stannous chloride and14.4 g (0.05 mole) of sodium salt of 4-hydroxydodecane sulfonic acidwere placed with 50 ml of xylene. The thus obtained mixture wassubjected to l5-hours' reflux, and

thereafter it was treated in the same way as in Example 1, whereby wasobtained urethanated sodium salt of hydroxydodecane sulfonic acid.

EXAMPLE 3.

In a three-neck flask equipped with reflux condenser, stirrer andthermometer, 60 g (0.1 mole) of urea and 18.0 g (nearly 0.05 mole) ofsodium salt of C a-olefine sulfonic acid (including 55 percent hydroxysulfonate) were placed with 50 ml of toluene. The thus obtained mixturewas subjected to 30-hours reflux, and thereafter, toluene was distilledout therefrom under reduced pressure.

The nitrogen analysis of the thus obtained urethanated product provedthat said product included 50.1 percent of urethanated hydroxysulfonate.

What is'claimed is:

l. A method for urethanation of hydroxyalkane sulfonates expressed bythe following general formula, (I), comprising the steps of conductingreaction between said hydroxyalkane sulfonate and urea in an inertorganic solvent in the molar ratio of l 1.0 4.0 at a temperature withinthe range of 100 180 C; and recovering carbamic acid ester of hydroxyalkane sulfonate expressed by the following general formula, (ll) fromreaction mixture resulted from said reaction.

R2 RrCH-R:rH-SO3M OH (I) wherein R represents alkyl radical, Rrepresents hydrogen or alkyl radical, (but the sum total of carbon atomspossessed by both R and R is 3 21), R represents absence or alkyleneradical having one to three carbon atoms, and M represents alkali metal,alkali earth metal, ammonium, or substituted ammonium.

R2 R CIIR.zC lH-SOnM IIzNC Oz (ll) 2. A method for urethanation ofhydroxyalkane sulfonates according to claim 1, wherein urethanation iscarried out at a temperature within the range of C.

3. A method for urethanation of hydroxyalkane sulfonate according toclaim 1, wherein the hydroxyalkane sulfonate to urea molar ratio is +11.2 3.0.

4. A method for urethanation of hydroxyalkane sulfonates according toclaim 1, wherein an inert organic 5 solvent is aromatic hydrocarbonselected from the group consisting of benzene, toluene, xylene andmixtures thereof.

2. A method for urethanation of hydroxyalkane sulfonates according toclaim 1, wherein urethanation is carried out at a temperature within therange of 120* - 140* C.
 3. A method for urethanation of hydroxyalkanesulfonate according to claim 1, wherein the hydroxyalkane sulfonate tourea molar ratio is +1 : 1.2 - 3.0.
 4. A method for urethanation ofhydroxyalkane sulfonates according to claim 1, wherein an inert organicsolvent is aromatic hydrocarbon selected from the group consisting ofbenzene, toluene, xylene and mixtures thereof.